Process for the conversion of hydrocarbons



Feb. 6,- 1940. M. PQ YouKER 2,189,645

PROCESS FOR THE CONVERSION OF HYDROOARBONS Filed Feb. 11, 1935 2 Sheets-SheeI '1 Feb. 6,V 1940. M. P. YOUKER PROCESS FOR THE CONVERSION OF HYDROCARBONS 1935 Z2 Sheets-Sheet Filed Feb. 11

NN Om IN V E TOR.

A TTORNE YS.

@atented Feb. 6, i

UNITED STATES rATsNT orma PROCESS ron m -eoNvsasIoN o maocaanons Application February 11,' 1935,'Serial No. 6,124

19 Claims.

, y ess whereby an increased yield of normally liquid hydrocarbons may be obtained.

In another of my patents, namely No. 1,962,107, I have disclosed an improved method of fractionation which is particularly useful in connection` with the aforesaid polymerlzing process, in that it provides for an eflicient and economical method of separating the normally gaseous from the normally liquid products of the polymerizing process. This improved method of fractionation comprises broadly the steps of first fractionating the products of the polymerizing process under relatively high superatmospheric pressure to sharply separate the normally gaseous hydrocarbons from the normally liquid hydrocarbons and subsequently fractionating the normally liquid hydrocarbons under comparatively lower pressure to separate gasoline contained therein from the heavier products.

My present invention has for one of its principal objects the improvement in the above described fractionating process, which provides a method of economically recovering, in liquid form, a substantial portion of the normally gaseous hydrocarbons separated in the first fractionating step which are desirable as recycle stock for the polymerizing process in order to increase the over-all yield of normally liquid hydrocarbons from the process. L

Several methods of accomplishing this principal object will be presented in the following disclosure.

One such method provides a process for utilizing the energy contained in the compressed gaseous products of polymerization to effect cooling of the gaseous products and utilizing the resulting cooled gaseous products to assist in condensation of the said gaseous products in order to recover a maximum quantity of liqueflable constituents of the gaseous products.l In this method the invention consists broadly in making double use of the pressure developed in the polymerization of the nor- (Cl. 19d-153) condensed and the resulting condensate returned to the polymerizing step. Another method includes absorption of constituents oi the gaseous products of polymerization in relatively heavy oil followed by introduc- 'l tion ofthe enriched absorption oil to the fractionating system either by way oi the transfer line from the polymerization zone or by direct introduction into the high pressure fractionating step.

Still a third method originally disclosed broadly in my pending application Serial No. 481,318, now Patent No. 2,027,460, provides for the controlled introduction of relatively large quantities of heavy oil into the high pressure fractionatlng step either directly or by way of the transfer line from the polymerizing zone in order to absorb a large portion of the excess heat contained in the products of polymerization thereby condensing a considerable portion of the vaporous products of polymerization, and thus effecting, under controlled 20 conditions, such changes in the composition of the vaporous products as to permit the high pressure fractionator to operate at greatly improved eiiiciency.

This latter method is not to be confused with the ordinary method of introducing relatively cool oil into the transfer line of a cracking process for the .purpose of stopping the cracking reaction and preventing the formation and deposit of coke in the transfer line. While my method may' also l accomplish this particular result, I contemplate using quantities of oil greatly in excess of that 'used in stopping a cracking reaction. For example in my process I may introduce 4,000 to ,6,000- barrels per day of heavy oil into the transfer line or high pressure fractionator of a gas polymerization process charging 6,000 barrels per day of normally gaseous hydrocarbons in a liquid phase such as butane whereas in oil cracking processes the amount of oil introduced for the purpose of stopping the cracking reaction is usually less than 2,000 barrels'per day for 6,000 barrels of charging oil per day.

The importance of this will be evident from the followingdiscussion of gas polymerization. In the polymerization of gases such butane and propane to liquid products in-the gasoline and heavier range, temperatures of about 1,000" F. or higher are usually employed depending upon the pressure used which is usually 1,000-3,000 per square inch. At 'such temperatures, the products leaving the transfer line are almost entirely vaporous and because of the type\of charge and nature of the products, will contain a large proportion of normally' gaseous materials such as butane and propane, which, as a result of the high temperatures employed. will be heated to temperatures greatly in excess of their critical temperatures and regardless of the pressure 45 maintained on the fractionator a very large A quantity of reflux will be required at the top of the fractionator to cool these gases below their critical temperature so that sumcient condensation for proper fractionation to separate butane l and lighter gases from heavier materials may oocur. In other words under such conditions the materials in the fractionating tower will be in gaseous condition during their passage through the major yportion of the tower and only a relatively small section of the fraotionating tower, that near the upper portion, will be able to serve as an efficient fraotionating device, and then only when a very large quantity of top reflux is used. By my method of introducingy a very large quantity of relatively heavy oil into the high pressure fractionator, I am able to condense and absorb substantially all of the constituents of the products of polymerization which are heavier than butane while at the same time I will so reduce the temperature of the remaining vaporous material, that a much smaller quantity of top renux will be required and a much larger section of the fractionator will come into use as an efficient fractionating device, and thus enable me to obtain a greatly improved separation between butane and propane and heavier products. Since the -recycle stock for Vthe gas polymerization process is preferably butane a good method of separation is greatly to be desired in order to obtain a maximum yield of gasoline from the butane in the charging stock.

Other objects and advantages of my new invention will become apparent in view oi the following description taken in commotion with the j attached drawings.

Figure 1 is a diagrammatic arrangement of one form of apparatus that may be used in conducting my improved process.

Figure 2 illustrates diagrammatically another g, form of apparatus for accomplishing the aforesaid principal object of my invention, in particular by the second and third methods described above. Referring to Figure l, a charging pipe I in which is mounted a pump 2 leads through a furnace 3 into a high pressure fractionator 4. A pressure control valve 5 is mounted in the pipe I between the furnace 3 and fractionator 4. A vapor outlet pipe 6 in which is mounted a valve 1 leads froml the upper portion of fractionator 4 55 through a condenser 9 and into a reux accumulator 9. Reflux accumulator 9 may be simply a separator or it may be a combined separator and bubble tower fitted with bubble plates 68 as illustrated. A pipe I8 in which is mounted a valve I I 00/ leads from the lower portion of accumulator 9 into the upper portion of fractionator 4. A second pipe I2 in which is mounted a valve I3 leads from the lower portion of accumulator 9 into charging pipe I. A coil 56 through which a heat- 05. ing fluid may be circulated is located in the lower portion of accumulatorll A pipe I4 in which is mounted a valve I5 leads from the upper portion of accumulator 9 through an auxiliary condenser I6 (high pressure side) into a liqueiled gas accu- 70l mulator I1 from the lower portion of which a pipe I8 in which is mounted a valve I9 leads back into the upper portion of accumulator 9. A second pipe 20 in which is mounted a valve 2l leads from the lower part of accumulator I1 into pipe l I2. A third pipe 22 in which is mounted a valve 23 leads from the lower portion of accumulator I1. A pipe 24 in which is mounted a valve 25 leads from the upper portion of accumulator I1 to a mechanical device 26, the function of which will be hereinafter described. A pipe 21 in which 5 is mounted a valve 28 leads from mechanical de- Vice 26 to auxiliary condenser I6 (low pressure side) from which a pipe 29 leads into an absorber 30. A pipe 3| in'which is mountedl a valve 32 leads from pipe 21 directly into pipe 29 providing l0 a by-pass around auxiliary condenser I6. A pipe 68 in which is mounted a valve 69 leads from the upper portion of absorber 30. A pipe 33 leads into the upper portion of absorber 30 and a pipe 34 in whichis mounted a pump 35 leads from the l5 lower portion of absorber 30 and connects absorber 30 with pipe I at a point between the furnace 3 and fractionator 4. A branch pipe 34a in which is mounted a valve 34a leads from pipe 34 into an intermediate portion of fractionator 4 at 20 a point above the point of entry of pipe I into fractionator 4. A branch pipe 34h in which is mounted a valve 34h' connects pipe 34 by way of pipe 34a into pipe I at a point between valve 5 and fractionator 4. A pipe 36 in which is mounted a 25 valve 31 leads from an intermediate portion of fractionator 4 to a low pressure fractionator 38.

A second pipe 39 in which is mounted a valve 48 leads from the lower portion of fractionator 4 into fractionator 38. A pipe 4I in which is 30 mounted a valve 42 leads from the lower portion v of fractionator 4 and connects -into a pipe 6I in which is mounted a valve 62 which connects to pipe I at a point between the furnace 3 and valve 5 or by way of pipe 63 in which is mounted a valve 35 64 into pipe I between valve 5 and fractionator 4.

A pipe 43 in which is mounted a valve 44 leads from the lower portion of fractionator 38 and connects into pipe 6I and a heating coil 61 is provided in the lower portion of fractionator 38. A pipe 45 in which is mounted a valve 46 leads from an intermediateportion of fractionator 38 and connects into pipe 6I. A pipe 65 in which is mounted a valve 66 also leads from pipe 45. A pipe 41 leads from the upper portion of fraction- 45 ator 38 through a condenser 48 into a gasoline receiver 49 from which a pipe 58 in which is mounted a valve 5I leads into the upper portion of fractionator 38. A pipe 52 in which is mounted a valve 53 leads from the lower portion of receiver 50 49 and a pipe 54 in which is mounted a valve 55 leads from the upper portion of receiver 49.

The apparatus above described will be used in carrying out my new improvements in the following manner.

Normally gaseous hydrocarbons, preferably under. sufficient pressure to maintain them in a liquid state, will be charged by pump 2 through pipe I which passes through a furnace 3 and thence into high pressure fractionator 4. While passing through that portion of pipe I which is within furnace 3 the normally gaseous hydrocarbon material will be heated and partially polymerized to gasoline and heavier materials. Pressure control valve 5 may be manipulated to main- 65 tain any desired pressure on the material in pipe I during its passage through furnace 3. A mixture of liquid and vapor will emerge from pipe I into fractionator 4 wh'ere a separation between vapor and liquid will be effected. Vapor will ow upwards through fractionator 4 which is preferably of the bubble tray type and will pass-from the upper portion of fractionator 4 through pipe 6 and valve 1 which will be manipulated to hold any desired pressure in the fractionator 4 and thence tile portion will usually consist principally ofk assesses through condenser d wherein a portion of the vapor will be condensed and condensate and uncondensed gases will then ow into reux accumulator t which will preferably be fitted with bubble trays @t in order that the accumulator 9 may serve as, a fractionator if desired, although this will not be necessary in all cases. .Heating iiuid may be passed through coil E8 which is located in the lower portion of accumulator t' to aid in fractionating the gas-fliquid mixture entering accumulator d from condenser it. A portion of the liquid which will collect in the lower portion of accumulator t will be returned through pipe l0 to the upper portion of fractionator t and valve II will be utilized to control the quantity of liquid so returned so as to condense within the fractionator .t substantially all the gasoline and heavier constituents contained in the vapors flowing upward through the fractionator t.

By controlling the fractionation in fractionator t so that substantially all the gasoline and heavier materials contained in the vapors flowing upward in the iractionator will be condensed therein, the gases leaving the top of fractionator 4 will consist of hydrocarbons lighter than gasoline such as butane, propane and still lighter materials. As a result of the condensation effected in condenser t 'and the rectification eifected in accumulator 9 the liquid which will collect in accumulator 9 will consist principally of the less volatile portion oi.' thegases leaving fractionator 4. 'I'his less volabutane.

Liquid which will collect in accumulator 9 in excess of that which will be returned to fractionator E will pass through pipe I2 and valve I3 to pipe l where it will be mixed with the original charge and again pass through the polymerization I step.

The liquid returned from accumulator 9 to the fractionator 4 will ow downwards through the fractionator 4 and will condense the gasoline and heavier materials which will be withdrawn from the fractionator t through pipes 36 and 39, which will discharge the material so withdrawn into low pressure fractionator t9. Valves 39 and 4d will be manipulated to control the quantity of material withdrawn through pipes 99 and 39 respectively, Liquid material which will collect in the lower portion of fractionator 4 may be withdrawn to control the quantity of liquid entering pipe 9| v from fractionator 4,

The gases which will separate from the liquid in accumulator 9 will pass therefrom through pipe Id through auxiliary condenser i9 (high v pressure side) and into liqueiied gas accumulator I'I. A valve l5 mounted in pipe I4 may be manipulated to hold any desired pressure on the preceding portions of the fractionating system. In passing through the auxiliary condenser I3 a portion of the gases will be condensed and a mixture of liquid and gas will be delivered by the equipment through which the gases leaving accumulator il may be expanded in doing mechanical work. The gases as a result of doing mechanical work in expanding will become considerably cooled and the resulting cooled and expanded gases will pass from the mechanical device 28 through pipe 21 and valve 28 into auxiliary condenser i6 (low pressure side) and thence through pipe 29 into absorber tower 30.

A pipe 3l in which is mounted a valve 32- leads from pipe 2l around condenser IS yinto pipe 29. By closing valve 29 and opening valve 32 the cooled and expanded gases passingthrough pipe 21 may be Icy-passed around condenser I6 and passed directly to absorber tower30.

The cooled gases entering absorber tower 3G will pass upwards through absorber tower 30 and will pass therefrom through pipe 68 and valve 69. Absorption oil, such as gas oil or the like will be introduced into the upper portion of f tion oil into pipe I at a point between furnace 3 and valve l. Instead of entering pipe I between the furnace 3 and valve 5 theenriched absorption oil may be introduced into the fractionator 4 by way of pipe 34a or into pipe I between the valve 5 and fractionator 4 by way of pipe 34h. Valves 34', 34a', and 34h are provided in pipes 34, 34a, and 34h respectively for the purpose of controlling the quantity of liquid introduced at each-or all of the points described.

Of the liquid which will'collect in the lower part of accumulator I1 a portion thereof will be returned through pipe I8 and valve I9 to the upper part of accumulator 9 as refiuxliquid, and liquid in excess of that returned to accumulator 9 may pass through pipe 20 and valve 2| into pipe I2 and thus return to the polymerizing step, or a part of this liquid may lne-withdrawn from accumulator l1 through pipe 22 and valve 23 to be disposed of in some other mannen- Returning now to the low pressure iractionator 39 into which the gasoline and heavier productsfrom fractionator 4 will be introduced by means of pipes 39 and 39 as previously described. In passing from fractionator 4 to fractionator 38 the gasoline and heavier liquids will pass from a region of relatively high super-atmospheric pressure to a region of relatively low super-atmospheric pressure; for as pointed out in the introductory paragraphs of'the present application one of the features of the present invention is the fractionation of gasoline and heavier liq-r uids under lower pressure than that maintained during the fractionation of all of the products oi polymerization wherein the gases are initially separated from gasoline and heavier liquid leaving fractionator 4. Vaporization of the gasoline 6 and heavier liquid will take place in fractionator 33 and vapors containing substantially all of the gasoline will separate from unvaporized liquid and will flow upward through fractionator 33 and those vapors which reach the top of fractionator 39 will pass therefrom through pipe 41, and condenser 9 into gasoline receiver 49. A heated uid may be circulated through heating coil 6l' to aid in vaporizing the gasoline contained in the liquid collecting in the lower portion of fractionator I8. In passing through condenser 48 the vapors will be at least partially v hold any desired pressure on the low pressure fractionating system which includes fractionator 3l, condenser 48, receiver 49. and their interconnecting pip'es. A portion of the gasoline which will collect in receiver 4l will pass through pipe ll and will be returned to the upper portion of fractionator I8 to serve as reilux. Valve .5I mounted in pipe 50 will be manipulated to control the quantity of gasoline returnedto fractionator 38 to control the fractionation therein so that all material heavier than gasoline will be condensed within fractionator 38 and only gasoline and lighter vapors will remain uncondensed therein. Gasoline which will collect in receiver 49 in excessof that necessary for refluxing fractionator 38 will be withdrawn from receiver 49 through pipe 52 and valve 53 and will be delivered to storage, not shown, as a ilnal product condensed within fractionator 38 may be with-- drawn from fractionator 38 and may be passed into pipe 6I for introduction into pipe I, or such distillates may be withdrawn from the process by way of pipe 65 in which is mounted valve 6B. Liquid which will collect in the lower portion of fractionator 88 will be withdrawn therefrom through pipe 43 and valve 46 and may also be discharged into pipe 6I.

As indicated by the above description, the material passing through pipe 6I to fractionator 4 by way of pipe I may be withdrawn either from the bottom of fractionator 4, the bottom of fractionator 38 or from an intermediate por- Y tion ofA fractionator $8. The quantity and type liquid thus returned, whether distillate oils or heavier, will depend upon the temperature employed in the polymerization step, the conditions desired in the fractionator 4, etc.` As previously indicated above, the quantity of oil introduced into the fractionator 4 may be substantially equal to the quantity of m'aterial charged to,

the polymerizing process. This particular relationship, while useful in some cases, is not fixed and may vary with conditions as indicated.

but in every case the quantity of oil fed into the 'pipe I from pipe BI will be substantially greater than that necessary to merely stop the conversion reaction to prevent deposition of carbon in pipe I and fractionator 4.

f The temperature to whichthe normally gaseous hydrocarbons are heated in orderl to effect polymerization thereof will usually lie within the range 750 to 1250 F. and in some cases higher or lower depending Aupon the type of rcharging` stock, whether relatively saturated or unsaturated. the yield per pass desired, the presinch. While therange ci pressures usually employed lies between 1000 and 3000 pounds per square inch useful results may be obtained with-l in the broader range and the particular pressure employed will be dependent upon the various factors indicated.

The pressure maintained on that portion of the fractionating system comprising fractionator 4, condenser 8, accumulator 9, condenser I 6 (high pressure side) accumulator I1 and the interconnecting pipes will most usually be between 200 and 600 pounds per square inch, the particular pressure depending upon the degree of fractionation desired, the temperature of the vapors to be fractionated, etc. The pressure in the condenser 8 and accumulator 9 may be lower than that in fractionator 4 if desired, and by manipulation of valves 1 and I5 any desired pressure or combination of pressures may be maintained on this portion of the fractionating system. Likewise condenser I 8' (high pressure side) and accumulator I1 may be maintained at the same or lower pressure than accumulator 9, and valve may be manipulated so as to control this pressure as desired.

In passing through the mechanical device 26 the pressure on the gases leaving accumulator I1 may be reduced to substantially atmospheric or to a pressure suicient merely to force the expat :led gases through the succeeding portions of the apparatus. The absorber 30 will usually be under this reduced pressure and valve 32 will be manipulated to regulate the pressure in these parts of the equipment.

Mechanical device 26 together with condenser I6 illustrates a single stage expansion unit. Due

'to the usual presence of water vapor in the gases leaving accumulator I1 it will usually be found desirable to limit the degree of cooling to a temperature above 32 F. to avoid formation of ice and subsequent freezing up of the apparatus. In such cases multi-stage expansion will probably be necessary for control of the degree of cooling and a series of expansion units similar to that illustrated could be used. Where no water vapor is present single stage expansion' to obtain the maximum degree of cooling of the gases may be used.

The pressure maintained on fractionator 38, condenser 48 and accumulator 49 will be some pressure lower than that maintained on fractionator 4 and while this lower pressure will most frequently be substantially atmospheric it may be found desirable to hold a somewhat higher than atmospheric pressure, in fractionator 38, condenser 48 and accumulator 49. This pressure will be regulated by manipulation of valve 55.

'Ihe absorption oil passing through absorber 30 to pipe I or fractionator 4 may be oil withdrawn from fractionators 4 and/or 38 or it may be oil from another source. The absorption oil may consist of kerosene distillate, gas oil, or fuel oil as conditions dictate. Similarly the oil entering pipe I and fractionator 4 by way of pipe 6I may be obtained from some source outside the present process and the quantity introduced through pipe 6I may be less than that required in accordance with the description given above, the additional quantity required being supplied by that introduced into the pipe I or fractionator 4 by way of pipe 34. Under certain conditions it may be found desirable to supply all of the extraneous oil introduced into pipe I and fractionator 4 by way of absorber 30 and pipe 34 and to supply none of such oil through pipe El, or all the required oil may be introduced in to pipe I by. way of pipe 6I and none by way of pipe 34.

'arcanes .e

It will be-evident from the foregoing that l have disclosed a combination of steps for polymerizing normally gaseous hydrocarbons to'normally liquid hydrocarbons, which includes the step of supplylng suflicient relatively heavy oil to the pressure `fractionation step as described to obtain a sharp separation between the butane and lighter portion and the gasoline and heavier portion of the products of the polymerization, and a series -oi steps for eiiiciently fractionating the butane and lighter materials to .separate butane from propane and lighter 'and to recover substantially all of the butane therefrom in order that the maximum amount of recycle stock (butane) may be returned to the polymerizing step and thus obtain va maximum yield of gasoline and heavier products from .the original charge.

By practicing my invention by the above described process a maximum yield of gasoline and heavier materials will be obtained from the initial charge of butane or lighter hydrocarbons due principally to the series of steps utilized to recover the maximum amount of recycle stock from the products of polymerization. However I find that in certain cases, due to economic conditions, it may be desirable to simplify vthe major process somewhat at the sacriiice of .a small' portion of the possible yield. In such cases by eliminating vthe supercooling of the gases entering accumulator i 1, and the apparatus required therefor I may simplify the entire process at the cost of some recycle stock which would be recoverable by the process above described. Thus simplified the process would still result in improved yields over the processes outlined in my issued patents and pending application.

This simplified process will now be described in connection with Figure 2 of the attached drawings.

Referring to Fig. 2, normally gaseous hydrocarbons, preferably under suihcient pressure to maintain them in the liquid state, will be drawn through pipe 1l by pump 12 and charged thereby through polymerizing coil 13 mounted inY a fur. l

nace 14 into a high'pressure fractionator 15. A valve 16 mounted in the outlet of polymerizing coil 13 will be manipulated to maintain any desired pressure on the hydrocarbons undergoing polymerization in the coil 1S. In passing through polymerizing coil 13, the normally gaseous hydrocarbons will be subjected to sufficient heat generated in furnace 14 to polymerize at least a porwill pass therefrom through pipe 11 in which is mounted valve 18, and thence through condenser 19 wherein a portion of the vapors will be condensed and a mixture of condensate and unconf densed vapors will then iiow into accumulator which will preferably be fitted with bubble trays 8| and a collector plate 82. Heating fluid may be circulated through a coil 83 located in the lower portion of accumulator 80 to aid in separating uncondensed vapors from condensed liquid.l As a result of the temperature, pressure and reflux conditions maintained in fractionator 15 and accumulator 80 the liquid which will collect-in the lower portion of the accumulator will consist principally of butane and a portion thereof will liquid will be thus returned to condense substanv tially all material of thegasoline and heavier range from the vapors in fractionator 1t. a valve mounted in pipe 94 will be manipulated to control the amount of such refluxfreturned to frectionator1t. Liquid in excess of that returned to fractionator 15 will be withdrawn from the lower portion of accumulator 80 through a pipe it in which is mounted a valve 8l and returned to pipe 1i where it will be mixed with the originalcharge and again pass through the polymerizingcoil in order that additional quantities of gasoline and heavier products may be produced therefrom,

Gases'separated from the liquid in accumulator et will iiow upwards over collector plate 92 and bubble trays 9i and the gases reaching the upper portion of accumulator Bil will pass therefrom through pipe 98' in which is mounted a valve d@ which may be manipulated to control ythe press sure yin the preceding portion of the high presn sure fractionating system comprising fractionator 15, condenser 19, accumulator 80 and their interconnecting pipea Relatively heavy oil of the gas oil or distillate type will be fed through a pipe 99 in which is mounted a valve 90, by means of a pump 9i into the upper portion of accumulator 99 and will flow downwardly therein over bubble trays 9i and will contact the gases flowing upward through accumulator 80 and as a result of contact with the gases will absorb and condense additional liqueflable constituents therefrom. These liqueabie constituents will comprise the maior portion of the butane remaining in the gases after the initial separation in the lower portion of accumulator 80. This relatively heavy oil including the absorbed constituents of the gases will collect on collector plate 92 which will be so designed as to prevent any of the heavy oil reaching the lower portion of the accumulator 80 thus avoiding contamination of the butane reflux and recycle stock with heavy oil. The liquid collecting on collector plate 82 will be withdrawn from accumulator 90 through pipe 92 by pumpl 93 and will be pumped through pipe 94 into the outlet of polymerizing coil 13 and thence together with the products of polymerization into fractionator 15. Or the liquid passing through pipe 94 may pass directly into fractionator 15 by way of pipe .95.. Valves 95 and 91 mounted in pipes 94 and 95 respectively will be manipulated to control the quantity of heavy oil entering at either ci the described points. Introduction of this relatively heavy oil including the absorbed constituents into fractionator 15 will,v

among other things, permit the absorbed constituents to be vaporized in fractionatcr 15 due to contact with the high temperature products of polymerization introduced into fractionator 15 from coil 19. The vaporized constituents will then pass upward through fractionator 15 `and will pass therefrom through pipe 11 together with the butano and lighter, vapors from the polymerlzing coil 13 and will be condensed in condenser 19 and will increase the quantity of Valves and |02 located in pipes 66 and 99 respectively will be manipulated to regulate the quantities of liquid withdrawn through each of these pipes. As described above in connection with major process of this invention, fractionator |00 will be maintained under substantially lower pressure than fractionator 15. As a result of passing from a region of relatively high pressure toone of relatively low pressure the gasoline and heavier liquids which will enter fractionator |00 by way ofpipe 98 and/or 99 will at least partially vaporize and separate into vapors and liquid. The vaporization and separation being aided if necessary by circulating a heating fluid through a heating coil |03 located in the lower portion of fractionator |00. The vapors thus separated from unvaporized liquid will iiow upwards through fractionator |00 and the vapors comprising the gasoline and lighter products of the process reaching the upper portion of fractionator |00 will -ilow therefrom through a pipe |04, thence through a condenser |05 in which the gasoline contained in the vapors will be condensed and a mixture of liquid gasoline and uncondensed vapors will then flow from condenser |05 into a gasoline accumulator |06 in which uncondensed vapors will separate from liquid gasoline and pass from accumulator |06 through a pipe |01 in which is mounted a valve |08 which will be manipulated to regulate and maintain any desired pressure on the low pressure fractionating system comprising fractionator 00, condenser |05, accumulator |06 and their interconnecting pipes. A portion of the gasoline which will collect in accumulator |06 will be returned through a pipe |09 to the upper portion of fractionator |00 and a valve ||0 `mounted in pipe |09 will be manipulated to regulate the quantity of gasoline returned to fractionator |00 so as to effect condensation of all materials heavier than gasoline in fractionator 00. A pipe in which is mounted a valve ||2 leads from the lower portion of accumulator |06 and the gasoline product in excess ofthat required for refluxing fractionator |00 will be withdrawn through pipe to nal storage, not shown.

The materials heavier than gasoline contained in the vapors flowing upward in fractionator |00 will be condensed by contact with the reiiux in-l troduced into fractionator |00 from pipe |09 and will flow downwardly through the fractionator |00 and together with unvaporized liquid will be withdrawn from fractionator |00 through pipes |3 and/or I4 in which are mounted valves ||5 and ||6 respectively for the purpose of regulating the quantities of liquids so withdrawn. 'I'he liquids sowithdrawn may bev further utilized in the process as follows: The liquid withdrawn from fractionator |00 through pipe ||3 may be passed either alone or together with the liquid withdrawn through pipe ||4 by way of a pipe ||1 through a cooler ||8 and thence after cooling by way of pipe ||9 into pipe 39 through which it then enters accumulator 80 to serve aS the 'relatively heavy oil for the absorption of butane from the gases ilowingvupward through accumulator 80 as previously described. A valve is mounted in the outlet pipe of condenser ||6 and a v'alve |2| is mounted in pipe ||9 to provide for by-passin'g the cooler ||6 if desired.

Instead of utilizing the oil withdrawn from fractionator |00 as absorption oil in accumulator in the manner described, the oil may be passed from pipes ||3 and ||4 into and through pipes |22 and |23 respectively into a pipe |24, through which this oil, which may also be joined by heavy oil withdrawn from fractionator 16 through a pipe |25, is delivered into the outlet pipe of polymerizing coil 13. This oil may enter the outlet pipe of coil 13 either between the furnace 14 and valve 16 by wayof a pipe |26 or between the valve 16 and fractionator 15 by way of a pipe |21. Valves |23 and |29 mounted in pipes |26 and |21 respectively will be manipulated to regulate the quantity of oil entering either one or both of these points. Valves |30 in pipe |22, |3| in pipe |23, and |32 in pipe |25 will be manipulated to regulate the quantities of oil returned from either one or both of the fractionators 16 and |00 to the outlet of coil 13 vby way of pipe |24.

As described above in connection with Fig. 1 the quantity of oil returned through pipes 94 and |24 to fractionator 16 by way of the outlet` pipe of coil 13 will be relatively large in comparison with the quantity of oil necessary to merely stop the conversion reaction in the outlet to coil 13. 'I'his quantity will v'ary with the volume of charge to coil 13 and the temperature of polymerization. The ratio of such oil to the charge will vary usually between two volumes of oil to three volumes of charge per day and two volumes of oil to one of charge, although Athese particular ratios may also be further varied depending upon conditions. There is no critical relationship between the relative volumes of oil introduced by way of pipes 94 and |24; Where oil is introduced into the outlet of coil 13 through both pipes it will usually be found best to control the quantity entering by way of pipe 94 in accordance with the quantity needed for absorption purposes in accumulator 60. Any additional oil necessary in the outlet coil 13 can.then be supplied through pipe |24.

The temperature range employed in the polymerization reaction will be the same as described above in connection with the major process of this invention.

The pressures employed in polymerizing step and in the high and low pressure fractionating system will also be similar to those described in connection with the major process.

WhileI have described my' invention by reference to a number of different forms of apparatus in which it may be employed, I do not intend to be limited to such apparatus as it will be apparent to those skilled `in the art that many changes and modications may appropriately be made in the form and arrangement of apparatus without departure from the ysubstance of my invention which is dened in the appended claims.

I claim:

1. A process for the conversion of normally gaseous hydrocarbons to normally liquid hydrocarbons which comprises subjecting normally gaseous hydrocarbons to suitable conditions of temperature and pressure to eifect conversion of at least a portion thereof to normally liquid hydrocarbons, first rectifylng the products of conversion to sharply separate the normally gaseous from the normally liquid products, partially condensing the said normally gaseous products of conversion, separating the resulting condensate from uncondensed gases, returning a part of said condensate for reprocessing in said rectifying step, contacting the vsaid uncondensedv gases with a relatively heavy hydrocarbon oil to absorb additional constituents from said uncondensed gases and mixing the said heavy oil containing the absorbed constituents with said productsof conversion priorto said rst. rectifying step, all said rectiiying, separating. conclensing, and contacting stepsbeing carried out carbons to such conditions of temperature and v ducing into the resulting products of conver-A sion a relatively heavy hydrocarbon oil, passing said products of conversion andsaid heavy hydrocarbon oil into a separator and therein separating the resulting mixture into vapors lighter,

than gasoline and gasoline and heavier liquid products, returninga portion of said vapors lighter than gasoline for admixture with said relatively heavy hydrocarbon oil and introducing it together therewith into said resulting products of conversion, and condensing other portions of said vapors and returning a portion of the condensate thereof to said separator, and

4returning another portion of said condensate for reprocessing with the normally gaseous hydrocarbons originally charged.

- 3. `A process for converting normally gaseous hydrocarbons into normally liquid hydrocarbons, which comprises subjecting said gaseous hydropressure as will convert at least a portion thereof vinto normally liquid hydrocarbons, separating the products of said conversion into a liquid portion and a gaseous portion, passinga stream of hydrocarbon liquid in contact with said separated gaseous portion, and introducing said stream of hydrocarbon liquid and the gases absorbed therein into the products of said gaseous hydrocarbons after the same have been subjected to said temperature and pressure conditions. 4. A process for converting normally gaseous hydrocarbons into normally liquid hydrocarbons, which comprises subjecting said gaseous hydrocarbons to such conditions ofv temperature and pressure as wiltconvert at least a portion thereof into normally liquid hydrocarbons, rectifying the products of said conversion under relatively high super-atmospheric pressure to separate the same into a liquid portion and a gaseous portion, passing a stream of hydrocarbon liquid in contact with said separated gaseous portion to absorb a part thereof, and introducing said stream ot hydrocarbon liquid and the gases absorbed therein into the products of said gaseous hydrocarbons after the sameihave been subjected to said temperature and pressure conditions. 5. A process for converting normally gaseous hydrocarbons into normally liquid hydrocarbons, which comprises subjecting said gaseous hydrocarbons to such conditions of temperature and pressure as will convert at least a portion there-` of into liquid hydrocarbons, admixing with the products oij said conversion a hydrocarbon liquid having gases absorbed therein. separating said mixture into a liquid portion and a gaseous portion, segregating and collecting said gaseous por- I carbon liquid with said gases absorbed therein as the said liquid admixed with said products of conversion.

6. In the process for converting hydrocarbon gases which are normally gaseous at atmospheric temperatureand pressure into liquid hydrocarbon products boiling-within the gasoline range, the steps comprising scrubbing a ,dilute olenic gas containing hydrogen and methane with a hydrocarbon oil to form an enriched absorber oil, eliminating hydrogen, methane and undissolved gases from the system, passing the enriched absorber oil to a stripping zone and separating dissolved gasesfrom the enriched absorber oil by heating the same at an elevated pressure, liquefying a part of said separated gases while maintained under an elevated pressure by cooling, polymerizing said liqueiled gases into normally liquid hydrocarbon products in a heating zone at elevated temperatures and pressures,

. passing the polymerized -products from s aid heating zone intothe stripping zone, and separating unreacted gases from normally liquid hydrocarbon materials, withdrawing the normally liquid hydrocarbon materials from said stripping zone and separating therefrom liquid hydrocarbon products boiling Within they-gasoline range.

7. In the process for converting hydrocarbon gases which are normally gaseous at atmospheric pressure and temperature into normally liquid hydrocarbons boiling within the gasoline range, the steps comprising scrubbing normally gaseous hydrocarbons with a hydrocarbon oil to form an enriched absorber oil, eliminating undissolved gases from the system, passing the enriched absorber oil into a stripping zone and separating the dissolved gases from the absorber oil, polymerizing the gases separated iromthe absorber oil into liquid hydrocarbon products by heating the same inv a reaction zone to a temperature within therange of 900-1200 F. vwhile maintained at a pressure within the range of 500-3000 lbs. per squarel inch, passing the hot reaction products from the reaction zone into said stripping zone and separating unreacted gases from liquid hydrocarbon materials. withdrawing the normally liquid hydrocarbon materials from said stripping zone and separating therefrom liquid hydrocarbon products boiling within the gasolin range.

8. In a process for converting hydrocarbon gases which are normally gaseous at atmospheric pressure and temperature into normally liquid hydrocarbon materials, the steps comprising scrubbing normally gaseous hydrocarbons at elevatedv pressure with a hydrocarbon oil, eliminating undissolved gases from the system, separating dissolved 1gases from said hydrocarbon oil by heating the same at a pressure higher than the pressure at which they are absorbed in said hydrocarbon oil, liquefying a part of said sepa'- rated gases by cooling, polymerizing said liqueed gases into liquid products at temperatures of 900l200 F. and under pressures of 50o-3000 pounds per square inch, mixing with the hot polymerizcd reaction products .a portion of the enriched hydrocarbon absorber oil produced by scrubbing normally gaseous hydrocarbons with the hydrocarbon oil, passing the admixture into a separating zone, and separating the liquid products from unreacted gases. Y 9. In a process for converting hydrcarbon gases which are normally gaseous at atmospheric pressure and temperature into normally liquid hydrocarbons boiling within the gasoline range, the steps comprising scrubbing said gases at elevated pressure with a. hydrocarbon oil of the gasoil to form an enriched absorber oil; eliminating undissolved gases from the system, separating dissolved gases from said enriched absorber oil by heating the enriched absorber oil while maintained at a pressure higher than the pressure at which the gases were absorbedl by said hydrncarbon oil, liquefying a substantial part ofsaid separated gases while under the higher pressure by cooling, polymerizing said liqueiied gases into liquid hydrocarbon products at temperatures oi 9001200 F. and under pressure of 50G-3000 lbs. per square inch, mixing the hot polymerized reaction products with a portion of the enriched absorber oil, passing the admixture into a separating zone and separating liquid products from unreacted gases.

10. In a process for converting hydrocarbon gases which are normally gaseous at atmospheric pressure and temperature into normally liquid hydrocarbons boiling within the gasoline range, the steps comprising scrubbing said gases at elevated pressure with a hydrocarbon oil to form an enriched absorber. oil, eliminating undissolved gases from the system, passing the enriched absorber oil to a stripping zone and separating dissolved gases from said enriched absorber oil by heating the same while maintained at a pressure higher than the pressure at which the gases were absorbed vin said hydrocarbon oil, liquefying a substantial part of said separated gases while under the higher pressure by cooling, polymerizing said liquefied gases into liquid hydrocarbons boiling within the gasoline range at temperatures of 900-1200 F. and under pressures of 50G-3000 lbs. per square inch, mixing the hot polymerized reaction products with a portion of the enriched absorber oil, passing the admixture into said stripping zone and separating liquid hydrocarbon products from unreacted gases.

11. In a process for converting normally gaseous hydrocarbons 'into normally liquid hydrocarbons boiling within the gasoline range, the steps comprising scrubbing normally gaseous'hydrocarbons at an elevated pressure with a hydrocarbon oil to form an enriched absorber oil, eliminating undissolved gases from the system, passing the .fenriched absorber oil into a stripping zone and separating dissolved gases from said enriched oil by heating the same while maintainedn at a pressure higher than the pressure at which the gases wereabsorbed in said hydrocarbon oil. liquefyi'ng a substantial part 'of said separated gases while under the higher pressure by cooling,

bon boiling within the gasoline range, the steps: comprising scrubbing normally gaseous hydrocarbons atan elevated pressure with a hydrocarbon oil t9' form an enriched absorber oil, eliminating .undissolved gases from the system, passing the enriched absorber oil into a stripping zone and separating dissolved gases from said enriched oil by heating the same while maintained at a pressure higher than the pressure at which the gases were absorbed in said hydrocarbon oil, liquefying a substantial part of said separated gases while under the higher pressure by cooling, polymerizing said liqueiied gases in a heating zone attemperatures oi 9001200 F. vand under pressures of 500-3000 pounds per square inch into normally liquid hydrocarbon products boiling within the gasoline range, mixing the hot reaction products from the heating zone with a portion of the enriched absorber oil, passing the admixture into the stripping zone and withdrawing unreacted gases from the top of said stripper, withdrawing the liquid products from the lower part of said stripping zone and separating therefrom normally liquid hydrocarbons boiling within the gasoline range.

13. In a process for converting hydrocarbon gases which are normally gaseous at atmospheric pressure and temperature into normally liquid hydrocarbons, the steps comprising scrubbing normally gaseous hydrocarbons at an elevated pressure with a hydrocarbon oil to form an enriched absorber oil, eliminating undissolved gases from the system, separating the dissolved gases from the enriched absorber oil in a stripping zone by heating the enriched absorber oil while maintained at a pressure higher than the pressure at l which said gases were absorbed, liquefying a substantial part of said separated gases while under elevated pressure by cooling. polymerizing said liqueed gases in a heating zone into liquid hydrocarbons at elevated temperatures 90o-1200" F. and under pressures of 50G-3000 pounds per square inch, passing the reaction products from the heating zone into said stripping zone, withdrawing the liquid products from the lower part of said stripping zone and separating thereom the polymerized normally liquid hydrocar- 14. In a process for converting hydrocarbon gases which are normally gaseous at atmospheric temperature and pressures into normally liquid hydrocarbons boiling within the gasoline range, the steps comprising scrubbing hydrocarbon gases containing methane at an elevated pressure with a hydrocarbon oil to form an enriched absorber oil, eliminating uigdlssolved gases and methane from the system, assing the enriched absorber oil to a stripping zone and separatingdissolved gases from said enriched absorber Voill by heating vthe same while maintained at a pressure higher than the pressure at which the gases were absorbed in said hydrocarbon oil. liquefying a substantial part of said separated gases while under the higher pressure by cooling, polymerizing said liqueed gases in a reaction zone at elevated temperatures and pressures into liquid hydrocarbons,

mixing the hot reaction products from the reaction zone with a portion ofthe enriched absorber oil, passing the admixture into said stripping zone and separating unreacted gases from liquid hydrocarbon products, withdrawing said liquid hydrocarbon products from the stripping zone and separating therefrom liquid hydrocarbons boiling within the gasoline range.

15. 'I'he process of producing normally liquid low boiling gasoline-like hydrocarbons from relatively low boiling normally gaseous hydrocarbons which'comprises scrubbing a mixture of suchgases containing hydrogen, methane and higher boiling normally gaseous hydrocarbons having from two to four carbon atoms penmolecule with a relatively high boiling absorbent oil to effect the separation oi absorbed hydrocarbons having three or four carbon atoms per molecule from unabsorbed hydrogen and methane, removing the thereby enriched absorbent and introducing it with absorbed gaseous hydrocarbons into a stream of hot polymerized products from a gas-conversion operation to thereby partially cool said prducts and eiiect a stripping of absorbed constituents from the absorbent oil, removing the stripped absorbent oil, and returning at least al portion of the thus removed oil to the initial separating step for treatment of further quantities of gases, fractionating the commingled thereby cooled vaporous products from the gasconversion operation and the normally gaseous hydrocarbons removed in the stripping operation to recover a gasoline-like product, a lean gas fraction containing hydrogen and methane, and an intermediate fraction substantially free from hydrogen and methane and comprising principally gaseous hydrocarbons having three or four carbon atoms per molecule including previously absorbed gases contained in the absorbent oil, delivering said intermediate fraction without further distillation thereof to the aforesaid gas-con- 26 version operation where it is subjected to elevated temperature and pressure to efl'ect a conversion of said normally gaseous hydrocarbons to normally liquid products, and delivering the products from saidv gas conversion operation to 80 the stripping operation as aforesaid.

16. The process oi. producing normally liquid low' boiling gasoline-like hydrocarbons from relatively low boiling normally gaseous hydrocarbons which comprises scrubbing a mixture of such u gases containing hydrogen, methane and higher boiling normally gaseous hydrocarbons having from two to four carbon atomsiper molecule with a relatively high boiling absorbent oil to effect the separation of absorbed hydrocarbons having 40 three or four carbon atoms per molecule from unabsorbed hydrogen and methane, removing the thereby enriched absorbent and introducing it with absorbed gaseous hydrocarbons into a stream o! hot polymerized products from a gasconversion operation to thereby partially cool the said products and eect a stripping-of absorbed constituents from the absorbent oil, removing the stripped absorbent oil, fractionating the commingled thereby cooled vaporous prod- 50 ucts from the gas-conversion operation and the normally gaseous hydrocarbons removed in the stripping operation to recover a gasoline-like product, a lean gas fraction containing hydrogen and methane and a rich gas fraction substanl tially free from hydrogen and methane and comprising principally gaseous hydrocarbons having three or four carbon atoms per molecule including previously absorbed gases contained in the absorbent oil, delivering said rich gas fraction without further distillation thereof to the aforesaid4 gas-conversion operation for subjection as aforesaid to elevated temperature and pressure to eiect a conversion of `said normally gaseous' hydrocarbons to normally liquid products, deliveri ing the products from Asaid gas-conversion operation to the stripping operation as aforesaid, and returning said lean gas fraction to the scrubbing operation for recovery of gaseous polymerizable constituents and separation of hydrogen and methane. 5 17. In the manufacture or normally liquid gasoline-like products from normally gaseous hydrocarbons, the combination of steps which comprises subjecting a stream of normally gaseous hydrocarbons to elevated pressure and tempera- 10 ture suiicient to effect a conversionfthereof to normally liquid products, introducing normally gaseous hydrocarbons into an absorption zone, contacting said gases in said absorption zone with an absorbent hydrocarbon oil to thereby dissolve 15 normally gaseous hydrocarbons of from two to four carbon atoms in said oil, contacting the hot products of conversion with said'enriched absorbent oil to cool said products and strip normally gaseous hydrocarbons from said absorbent 20 oil, fractionating the thereby cooled products including said stripped gases to separate any constituents heavier than gasoline, gasoline-like products and normally gaseous hydrocarbons including those stripped from the absorbent oil,

and recycling normally gaseous hydrocarbons thus obtained without further distillation thereof to the conversion operation as charging stock therefor.

18. A process in accordance vwith claim 17 30 wherein the normally gaseous products separated from the products of conversion are divided into light and heavy fractions, the light fraction being returned to the absorption zone and the heavy fraction constituting the charge to the conversion operation. l

19. In the manufacture of normally liquid-gasoline-like products from normally gaseous hydrocarbons, the `combination of steps which comprises subjecting a stream o! normally gaseous 40 hydrocarbons to elevated pressure and temperature sunicient to eiect a conversion thereof to normally liquid products, contacting the hot products of conversion with an absorbent hydrocarbon oil containing a substantial amountV of 4.5

previously absorbed normally gaseous hydrocarbons to cool said products and strip the absorbed gases from the absorbent oil, fractionating the thereby cooled products including said stripped gases to separate any constituents heavier than gasoline, a gas fraction relatively lean in polymerizable constituents, a gas lfraction relatively rich in polymerizable constituents including previously absorbed gases contained in the absorbent voil and a gasoline-like fraction, 4delivering the relatively rich fraction without further distillation thereof to the conversion zone as aforesaid. scrubbing the"'rel`atively lean fraction with absorbent hydrocarbon oil to recover gaseous polylmerizable constituents therefrom, and employing the thereby enriched oil to directly contact and cool the hot products of conversion as aforesaid.

MALCOLM P. YOUKER.

1o f cERTIFcAT'E- 0FV CORRECTION.. PatentNo..' 2,l89,'6Li5. Februari 6, 19M).

v -mxLccLii LYOUKER.

Iris'hereby'.metflied thai; e'rror ,appearsf in the' prnted'pifcation l pf the abve numbered pgtvent requiring crrect'i'on s follows:A Page?,A :nc-v

Qnd-coim, line 75, 1iim'9,-ifar "hmmm-bon" eaaghjurrbn; page '8;

first colpmnf li-ne 5', after the ".011"- second .oc ciiniene, insert 12V-p95.- pag-e9.;A first cqlumni'lin'e 7, .claim -15`,V.for "prdncts" readprodiicts; and than; the said .Lettes .rekent-should befred with this gai-inaction therein t that the sme maymconfoz'm to th record of th case in t-:fne Patent Office@ signed am saale@ th'isfgatn damlofzipii'l, A.Y D. 19m.- 

